WO2010004988A1 - 電解銅箔および銅張積層板 - Google Patents
電解銅箔および銅張積層板 Download PDFInfo
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- WO2010004988A1 WO2010004988A1 PCT/JP2009/062362 JP2009062362W WO2010004988A1 WO 2010004988 A1 WO2010004988 A1 WO 2010004988A1 JP 2009062362 W JP2009062362 W JP 2009062362W WO 2010004988 A1 WO2010004988 A1 WO 2010004988A1
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- copper foil
- electrolytic copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1105—Heating or thermal processing not related to soldering, firing, curing or laminating, e.g. for shaping the substrate or during finish plating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12993—Surface feature [e.g., rough, mirror]
Definitions
- the present invention relates to an electrolytic copper foil excellent in flexibility and flexibility.
- the present invention also relates to a copper-clad laminate (hereinafter sometimes referred to as CCL) using the copper foil, and particularly to a copper-clad laminate suitable for high-density and high-functionality applications.
- CCL copper-clad laminate
- the bending angle (R) of the hinge part of a mobile phone tends to become smaller and smaller, the demand for the bending characteristics of CCL has become increasingly severe.
- the characteristics of the copper foil that are important for improving the bending properties include the thickness, surface smoothness, crystal grain size, and crystal orientation identity.
- adhesion (lamination) between the copper foil and the polyimide film is difficult, and the adhesive strength and flexibility of the copper foil attached to the polyimide film have become indispensable characteristics.
- a rolled copper foil that has been produced in a special manufacturing process and has many (200) plane crystal orientations is often used at present.
- the factor that improves the flexibility property is that there are many crystals having the same crystal orientation rather than the (200) plane being good.
- the copper foil having many (200) planes is all, and the electrolytic copper foil has a crystal structure in which each crystal orientation is randomly present.
- the appearance of an electrolytic copper foil having flexibility or flexibility equal to or higher than that of a rolled copper foil has been desired.
- the problem to be solved by the invention is to provide an electrolytic copper foil having flexibility or flexibility equal to or higher than that of a rolled copper foil, and to provide a CCL having flexibility and flexibility using the electrolytic copper foil.
- the electrolytic copper foil in the heat history applied when the electrolytic copper foil and the polyimide film are bonded, the mechanical properties and flexibility are improved, and the electrolytic copper for CCL can cope with the miniaturization of the electrical equipment. To provide a foil.
- the electrolytic copper foil of the present invention has an EBSP (Electron Backscatter Diffraction Pattern) analysis of the crystal structure after the electrolytic copper foil is heat-treated so that the LMP value (Larson-Miller parameter) shown in Formula 1 is 9000 or more. It is an electrolytic copper foil in which the color tone of either red or blue is 80% or more.
- Formula 1: LMP (T + 273) * (20 + Logt) Where 20 is the copper material constant, T is the temperature (° C.), and t is the time (Hr).
- the electrolytic copper foil of the present invention preferably has a relative strength of the (331) plane of 15 or more with respect to the (111) plane in the X-ray diffraction of the electrolytic copper foil after the heat treatment.
- the crystal structure after the heat treatment is 70% or more of crystal grains having a crystal grain size of 5 ⁇ m or more, and the (331) plane of the (111) plane in X-ray diffraction. It is desirable that the relative strength is 15 or more.
- the electrolytic copper foil of the present invention desirably has a tensile strength of 20 KN / cm 2 or less and a 0.2% proof stress of 10 KN / cm 2 or less after the heat treatment.
- Impurities contained in the cross section of the electrolytic copper foil are at least chlorine (Cl) less than 0.5% in intensity ratio with copper (Cu) in SIMS (Secondary Ion Mass Spectrometry) analysis in the depth direction of the copper foil cross section, It is desirable that nitrogen (N) is less than 0.005% and sulfur (S) is less than 0.005%.
- the copper clad laminate of the present invention is a copper clad laminate in which the electrolytic copper foil is laminated on an insulating substrate.
- the present invention can provide an electrolytic copper foil having flexibility or flexibility equal to or higher than that of a rolled copper foil. Moreover, this invention can respond
- the mechanical history and the flexibility are improved in the thermal history applied when the electrolytic copper foil and the polyimide film are attached, and the electrolytic copper for CCL can cope with the miniaturization of the electric equipment.
- the foil can be provided at a lower cost than the rolled copper foil.
- FIG. 1 is an EBSP same-system crystal range diagram.
- electrolytic copper foil is made by an electrolytic foil making apparatus.
- the electrolytic foil making apparatus comprises a rotating drum-shaped cathode (the surface is made of SUS or titanium), and an anode (lead or noble metal oxide-coated titanium electrode) arranged concentrically with respect to the cathode.
- current is passed between the two electrodes while supplying the electrolytic solution to deposit copper to a predetermined thickness on the cathode surface, and then the copper is peeled off from the cathode surface in a foil shape.
- the copper foil at this stage may be referred to as untreated copper foil.
- the surface of the untreated copper foil in contact with the electrolyte is called a mat surface, and the surface in contact with the rotating drum-like cathode is called a glossy surface (shiny surface).
- a foil manufacturing apparatus that employs a rotating cathode
- copper foil may be manufactured by a foil manufacturing apparatus that uses a cathode as a plate.
- copper is deposited on the drum-like cathode or the plate-like cathode to produce a copper foil.
- the surface roughness of the cathode on which the copper is deposited is such that the surface roughness of the shiny surface of the electrolytic copper foil of the present invention is Rz: 0.1 to 2.0 ⁇ m by using a cathode with Rz: 0.1 to 2.0 ⁇ m. It can be. Making the surface roughness Rz of the electrolytic copper foil 0.1 ⁇ m or less is difficult to manufacture in view of the cathode polishing technique and the like, and is considered impossible to manufacture in mass production.
- the surface roughness is Rz of 2.0 ⁇ m or more, the bending characteristics are extremely deteriorated, and the characteristics required by the present invention cannot be obtained, and at the same time, it is difficult to make the mat surface roughness 1.5 ⁇ m or less. is there.
- the roughness of the matte surface of the electrolytic copper foil is Rz: 0.1 to 1.5 ⁇ m. A roughness of 0.1 ⁇ m or less is very difficult even if bright plating is performed, and cannot be practically manufactured.
- the upper limit of the roughness is preferably 1.5 ⁇ m.
- the roughness of the shiny surface and the mat surface is preferably Rz: 1 ⁇ m or less.
- the surface roughness Ra of the shiny surface and the matte surface is preferably Ra: 0.3 ⁇ m or less, and most preferably Ra: 0.2 ⁇ m or less.
- the thickness of the electrolytic copper foil is preferably 3 ⁇ m to 210 ⁇ m. This is because a copper foil having a thickness of 2 ⁇ m or less cannot be manufactured well due to handling techniques and the like and is not realistic.
- the upper limit of the thickness is about 210 ⁇ m based on the current usage state of the circuit board. This is because it is unlikely that an electrolytic copper foil having a thickness of 210 ⁇ m or more is used as a copper foil for circuit boards, and the cost merit of using the electrolytic copper foil is lost.
- examples of the copper electrolyte for depositing the electrolytic copper foil include a copper sulfate plating solution, a copper pyrophosphate plating solution, and a copper sulfamate plating solution, but a copper sulfate plating solution is preferable in view of cost. .
- the copper sulfate plating solution preferably has a sulfuric acid concentration of 20 to 150 g / l, particularly 30 to 100 g / l.
- the sulfuric acid concentration is less than 20 g / l, it becomes difficult for current to flow, so that practical operation becomes difficult, and the uniformity of plating and electrodeposition also deteriorate.
- the sulfuric acid concentration exceeds 150 g / l, the solubility of copper is lowered, so that a sufficient copper concentration cannot be obtained, and realistic operation becomes difficult. Also, corrosion of equipment is promoted.
- the copper concentration is preferably 40 to 150 g / l, particularly 60 to 100 g / l.
- the copper concentration is preferably 40 to 150 g / l, particularly 60 to 100 g / l.
- the copper concentration is less than 40 g / l, it becomes difficult to secure a current density that allows practical operation in the production of an electrolytic copper foil.
- Increasing the copper concentration above 150 g / l is not practical because a very high temperature is required.
- the current density is preferably 20 to 200 A / dm 2 , particularly preferably 30 to 120 A / dm 2 .
- the current density is less than 20 A / dm 2 , production efficiency is very low in the production of electrolytic copper foil, which is not realistic. This is because, in order to increase the current density from 200 A / dm 2 , a considerably high copper concentration, a high temperature, and a high flow rate are required, which imposes a large burden on the electrolytic copper foil manufacturing facility and is not realistic.
- the electrolytic bath temperature is preferably 25 to 80 ° C, particularly 30 to 70 ° C.
- the bath temperature is less than 25 ° C., it is difficult to secure a sufficient copper concentration and current density in the production of the electrolytic copper foil, which is not realistic. Further, raising the temperature from 80 ° C. is very difficult in operation and facilities and is not realistic.
- chlorine is added to the electrolytic solution as necessary.
- the chlorine concentration is preferably 1 to 100 ppm, particularly preferably 10 to 50 ppm.
- the above electrolysis conditions are adjusted from the respective ranges for convenience so as not to cause defects such as copper deposition and plating burns.
- the copper sulfate plating bath for producing an electrolytic copper foil includes one or more di- or polyhalogenated chain aliphatic saturated hydrocarbon compounds, or one or two or more di- or polyhalogenated chain aliphatic saturated carbonizations having an ether bond.
- One or more hydrogen compounds, or one or more di- or polyhalogenated aliphatic saturated hydrocarbon compounds and one or more di- or polyhalogenated aliphatic saturated hydrocarbon compounds having one or more ether bonds The reaction product of the combination and the heterocyclic compound having two nitrogen atoms is added as a leveler.
- the carbon number of the di- or polyhalogenated chain aliphatic saturated hydrocarbon compound is generally 1 to 30, preferably 2 to 18, and more preferably 4 to 8.
- the carbon number of the di- or polyhalogenated chain aliphatic saturated hydrocarbon compound having one or more ether bonds is generally 4 to 30, preferably 4 to 12, and more preferably 6 to 10.
- 2,2′-dichloroethyl ether, 1,2-bis (2-chloroethoxy) ethane, diethylene glycol bis (2-chloroethyl) ether, triethylene glycol bis (2-chloroethyl) ether, 2,2 Examples include '-dichloropropyl ether, 2,2'-dichlorobutyl ether, tetraethylene glycol bis (2-bromoethyl) ether, heptaethylene glycol bis (2-chloroethyl) ether, and tridecaethylene glycol bis (2-bromoethyl) ether. It is done. These compounds are used alone or in combination.
- Heterocyclic compounds having two nitrogen atoms include piperazine, triethylenediamine, 2-methylpiperazine, 2,6-dimethylpiperazine, 2,5-dimethylpiperazine, homopiperazine, 2-pyrazolin, imidazole, 2-methyl Imidazole, 2-ethylimidazole, 2-propylimidazole, 4-methylimidazole, histidine, 1- (3-aminopropyl) imidazole, 2-imidazoline, 3-imidazoline, 4-imidazoline, 2-methyl-2-imidazoline, pyrazole 1-methylpyrazole, 3-methylpyrazole, 1,3-dimethylpyrazole, 1,4-dimethylpyrazole, 1,5-dimethylpyrazole, 3,5-dimethylpyrazole, benzimidazole, indazole, piperazine, 2-methylpipe Jin, 2,5-dimethylpiperazine, pyrimidine, pyridazine, and the like.
- 2-pyrazoline, pyrazole, imidazole, 2-methylimidazole, 2-imidazoline, 3-imidazoline, 4-imidazoline, 2-methyl-2-imidazoline and the like are preferable.
- a combination of a di- or polyhalogenated aliphatic saturated hydrocarbon compound and a di- or polyhalogenated aliphatic saturated hydrocarbon compound having one or more ether bonds and two nitrogen atoms A reaction product of a heterocyclic compound having can be used.
- the above raw material compounds include aliphatic amino compounds such as dimethylamine, diethanolamine and ethylenediamine, aromatic amino compounds such as phenylenediamine, succinyl chloride, glutaryl chloride, fumaryl chloride, dichloroxylylene, phthaloyl chloride and the like.
- a product obtained by reacting a compound having a plurality of reactive groups as a third raw material can also be used.
- an epihalohydrin such as epichlorohydrin as the third reaction component because the desired effect of the reaction product cannot be obtained.
- the reaction temperature for producing the reaction product is from room temperature to 200 ° C, preferably 50 ° C to 130 ° C.
- the reaction time for producing the reaction product is from 1 hour to 100 hours, preferably from 3 hours to 50 hours.
- the reaction for producing the reaction product can be carried out without a solvent, but a solvent may be used.
- the solvent include alcohols such as methanol, ethanol, 1-propanol, isopropanol, t-butanol and 1-butanol, dimethylformamide, dioxane, tetrahydrofuran, methyl cellosolve, ethyl cellosolve, dimethyl cellosolve, diethyl cellosolve and the like.
- halogen may be generated during the reaction, but the reaction may be carried out while containing the halogen, but it is preferable to use a known method such as ion exchange. It is also possible to obtain a halogen-free reaction product by a method of removing it by insolubilization or a method of insolubilizing and removing it as an alkali metal halide by reaction with an alkali metal hydroxide or the like. Whether a reaction product containing halogen or a halogen-free reaction product is adopted according to the performance as a copper electrolyte.
- the brightener used in the present embodiment may be appropriately selected from known ones.
- 3-mercaptopropanesulfonic acid and its salt, bis (3-sulfopropyl) disulfide and its salt, N, N-dimethyldithiocarbamine examples include acid (3-sulfopropyl) ester, N, N-dimethyldithiocarbamic acid (3-sulfoethyl) ester, sodium 3- (benzothiazolylthio) ethylsulfonate, pyridinium propyl sulfobetaine, and the like.
- polyethylene glycol having a molecular weight of 200 or more polypropylene glycol, a copolymer of polyethylene glycol and polypropylene glycol, and the above three kinds of glycols C1 to C6 alkyl monoether, polyoxyethylene glyceryl ether, polyoxypropylene glyceryl ether, polyoxyethylene polyoxypropylene glyceryl ether, and the like.
- Particularly preferred are those having a molecular weight of 500 to 100,000.
- the amount of each additive is added in the range of 0.1 to 1000 ppm while changing the amount and ratio.
- the additive added to the electroplating solution, particularly the leveler has a characteristic that it is not taken into the copper foil as an impurity.
- the crystal structure after the heat treatment with an LMP value of 9000 or more shown in the above formula 1 has a color tone in a range of either red or blue based on the surface by EBSP analysis.
- the copper foil occupies 80% or more, and its range is shown in FIG.
- a line was drawn perpendicularly to AC and the point where the line intersected AB was defined as Q, and the color tone was defined with the right side of the line as blue and the left as red.
- the color tone is less than 80%, the crystal is difficult to recrystallize, and when heat treatment is performed, the crystal does not become large, and crystals with different crystal orientations are present randomly. As a result, crystal slip and the like occur. This is because it tends to deteriorate and the flexibility becomes worse.
- X-ray diffraction of the above copper foil (X-ray analysis data was measured using an X-ray diffraction device of manufacturer name: Rigaku, device name: Geiger flex RAD-A (PC)) (111) surface
- a crystal having a (331) plane relative intensity of 15 or more and a blue color tone (specifically, the right blue range shown in FIG. 1) by EBSP analysis. It is preferable that it is a copper foil whose structure becomes 80% or more of the whole.
- At least chlorine (Cl), nitrogen (N), and sulfur (S) among the elements taken into the copper from the plating solution and the additive component are deep in the cross section of the copper foil.
- the strength ratio with copper (Cu) in SIMS (Secondary ⁇ Ion Mass ⁇ Spectrometry) analysis of each part in the vertical direction is at least chlorine (Cl) less than 0.5%, nitrogen (N) less than 0.005%, sulfur (S ) Is preferably less than 0.005%.
- oxygen (O) and carbon (C) it is more preferable that oxygen (O) is less than 1% and carbon (C) is less than 0.1%.
- the electrolytic copper foil of the present invention is a copper foil that is low in impurities and does not exist in part.
- the copper foil created above is an electrolytic copper foil in which 70% or more of crystal grains having a maximum length of 5 ⁇ m or more of each crystal grain are present by performing a heat treatment with an LMP value of 9000 or more shown in Formula 1. .
- Formula 1: LMP (T + 273) * (20 + Logt) Where 20 is the copper material constant, T is the temperature (° C.), and t is the time (Hr).
- the method for measuring the maximum length of crystal grains is to take a photomicrograph of a copper foil cross section, measure the maximum length of crystal grains in an area of 50 ⁇ m ⁇ 50 ⁇ m or an equivalent area, and the length is 5 ⁇ m or more.
- the area occupied by the crystal grains is measured, and it is confirmed by a method of calculating what percentage the measured area is relative to the area of the entire cross section.
- the relative strength of the (331) plane with respect to the (111) plane measured by X-ray diffraction is preferably 15 or more.
- a tensile strength of 20KN / cm 2 or less it is preferable 0.2% proof stress is 10KN / cm 2 or less.
- the proof stress is optimally 8 KN / cm 2 or less.
- a surface treatment layer is provided on at least one surface of the electrolytic copper foil.
- Specific examples include a roughened layer for the purpose of improving adhesion due to the anchor effect and a surface-treated layer for the purpose of adhesion, heat resistance, chemical resistance and rust prevention.
- the roughening layer is not an essential treatment as long as the surface treatment layer can achieve the target performance.
- examples of the metal surface treatment layer include Ni, Zn, Cr, Si, Co, and Mo alone, alloys thereof, or hydrates.
- the treatment to be deposited as an alloy layer after depositing at least one metal of Ni, Si, Co, Mo, or an alloy containing one metal, Zn is deposited and Cr is deposited.
- the thickness of the metal such as Ni or Mo that deteriorates the etching property is 0.8 mg / dm 2 or less. Even when Ni or Mo is precipitated as an alloy, the thickness is preferably 1.5 mg / dm 2 or less.
- Zn when Zn is attached in a large amount, it may melt during etching and cause deterioration of peel strength, so that it is preferably 2 mg / dm 2 or less.
- ⁇ ⁇ ⁇ Silane is applied on these metal surface treatment layers.
- the silane to be applied include commonly used amino, vinyl, cyano group, and epoxy systems.
- an amino or cyano group silane shows an effect of increasing the peel strength.
- the electrolytic copper foil which performed these processes is affixed on a film, and it is set as a copper clad laminated board.
- Foil making Examples 1-5, Comparative Examples 1-3 Table 1 shows the manufacturing conditions such as the electrolyte composition. After the copper sulfate plating solution having the composition shown in Table 1 is passed through an activated carbon filter and cleaned, the additives shown in Table 1 are added to obtain a predetermined concentration, and then a rotating drum type foil making apparatus with the current density shown in Table 1 To produce an untreated electrolytic copper foil having a thickness of 18 ⁇ m.
- the prepared untreated electrolytic copper foils of each Example and each Comparative Example were divided into three samples, and one sample was used to measure the amount of impurity elements contained therein and the surface roughness. Moreover, it heat-processed using the said unused sample, the cross-sectional crystal grain observation, the EBSP analysis, the X-ray diffraction, and the tension test were done. Finally, the remaining one unused sample was subjected to thermocompression bonding with a polyimide sheet to perform a bending test. Details of each measurement and test are described below.
- the amount of impurity elements inside the untreated electrolytic copper foils of Examples 1 to 5 and Comparative Examples 1 to 3 was measured by digging in the depth direction in SIMS analysis.
- the measurement elements are oxygen (O), carbon (C), chlorine (Cl), nitrogen (N), and sulfur (S).
- the measurement conditions of SIMS analysis are primary ions :: Cs + (5 kV, 100 nA) Secondary ion: Copper (Cu) 63 Cu -- Chlorine (Cl) 35 Cl -- Nitrogen (N) 14 N + 63 Cu -- Sulfur (S) 34 S -- Oxygen (O) 16 O -- Carbon (C) 12 C - Sputtering area: 200 ⁇ m ⁇ 400 ⁇ m I went there.
- the measurement was started after sputter removal from the surface to the depth direction of 2 ⁇ m, and the analysis was performed to the depth of 4 ⁇ m.
- the strength ratio was calculated from the average value of the strength of each measurement element and the average value of the strength of copper. The calculation results of the intensity ratio are shown in Table 2.
- the surface roughness Rz, Ra of each untreated electrolytic copper foil of each example and each comparative example was measured using a contact type surface roughness meter.
- the surface roughness Rz and Ra are defined in JIS B 0601-1994 “Definition and display of surface roughness”.
- Rz is “ten-point average roughness”
- Ra is “arithmetic average roughness”.
- the reference length was 0.8 mm. The measurement results are shown in Table 2.
- the amount of impurity elements in Examples 1 to 5 was smaller than that in the comparative example, and the surface roughness Rz was 1.0 ⁇ m or less for both the matte surface and the shiny surface. Further, as apparent from Table 3, in Examples 1 to 5, the ratio (%) of crystal grains existing in a length of 5 ⁇ m or more is 70% or more, and the ratio of a single (blue) color tone is determined by EBSP analysis.
- the relative intensity [(331) intensity ⁇ 100 / (111) intensity] in X-ray diffraction is 15 or more.
- the tensile strength is 20 KN / cm 2 or less
- the 0.2% proof stress is 10 KN / cm 2 or less
- the number of bendings is twice or more that of the conventional example.
- the state of the bending property has changed somewhat due to the causal relationship such as the impurity distribution ratio, crystal grain size, and the same crystal orientation system
- the bending property is clearly improved compared to the copper foil of the comparative example.
- the present invention can provide an electrolytic copper foil having flexibility or flexibility equal to or higher than that of a rolled copper foil. Moreover, this invention can respond
- the mechanical history and the flexibility are improved in the thermal history applied when the electrolytic copper foil and the polyimide film are attached, and the electrolytic copper for CCL can cope with the miniaturization of the electric equipment.
- the foil can be provided at a lower cost than the rolled copper foil.
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Abstract
Description
また、本発明は前記銅箔を使用した銅張積層板(以下CCLということがある)に関するもので、特に高密度・高機能用途に適した銅張積層板に関するものである。
屈曲特性を向上させる上で重要な銅箔の特性としては、厚さ・表面平滑性・結晶粒の大きさ・結晶方位の同一性などが上げられる。また、電気製品の小型化に対し、高密度配線化が図られるために、できるだけスペースを有効活用することが重要な課題であり、CCLの変形が容易に可能なポリイミドフィルムの採用が不可欠となってきている。しかし、銅箔とポリイミドフィルムとの接着(積層)はなかなか難しく、ポリイミドフィルムに貼り付ける銅箔の接着強度・柔軟性は必要不可欠な特性になってきている。
しかしながら、屈曲性の特性を向上させる要因は(200)面がいいというよりむしろ同一な結晶方位の結晶が多く存在することに要因があると考えられる。
現状では、上記したように圧延箔では(200)面の多く存在した銅箔がすべてであり、また電解銅箔にいたってはそれぞれの結晶方位が乱雑に存在する結晶構成になっており、従って圧延銅箔のような柔軟性・屈曲性を有する電解銅箔はなく、上記したように圧延銅箔と同等またはそれ以上の柔軟性・屈曲性を有する電解銅箔の出現が要望されていた。
このような要望に応えるためには電解銅箔の結晶配向が同一系のものが望ましいが、そのような銅箔は現状では開発されていないのが現状である。
式1:LMP=(T+273)*(20+Logt)
ここで、20は銅の材料定数、Tは温度(℃)、tは時間(Hr)
また、前記電解銅箔の少なくとも片方の面に密着性・耐熱性・耐薬品性・防錆を目的とした表面処理層が設けられていることが好ましい。
特に、電解銅箔においては、該電解銅箔とポリイミドフィルムとを貼り付ける際にかかる熱履歴において、機械的特性、柔軟性が改良され、電気機器の小型化に対し対応できるCCL用の電解銅箔を、圧延銅箔に比べて安価に提供することができる。
電解銅箔の表面粗さRzを0.1μm以下の粗さとすることは、カソードの研磨技術などを考えると製造が難しく、また量産製造するには不可能であると考えられる。また、Rzを2.0μm以上の表面粗さとすると屈曲特性が非常に悪くなり、本発明が求める特性が得られなくなると同時にマット面の粗さを1.5μm以下にすることが難しくなるためである。
電解銅箔のマット面の粗さは、Rz:0.1~1.5μmである。0.1μm以下の粗さは光沢めっきを行ったとしても非常に難しく現実的に製造は不可能である。また、上記したように電解銅箔の表面が粗いと屈曲特性が悪くなることから粗さの上限は1.5μmとすることが好ましい。
また、上記電解銅箔の厚みは、3μm~210μmであることが望ましい。厚さが2μm以下の銅箔はハンドリング技術などの関係上うまく製造することができず、現実的ではないからである。厚さの上限は現在の回路基板の使用状況からして210μm程度である。厚さが210μm以上の電解銅箔が回路基板用銅箔として使用されることは考え難く、また電解銅箔を使用するコストメリットもなくなるからである。
硫酸濃度が20g/l未満となると電流が流れにくくなるので現実的な操業が困難となり、さらにめっきの均一性、電着性も悪くなる。硫酸濃度が150g/lを超えると銅の溶解度が下がるので十分な銅濃度が得られなくなり現実的な操業が困難となる。また、設備の腐食も促進される。
銅濃度が40g/l未満となると電解銅箔の製造において現実的な操業が可能な電流密度を確保することが難しくなる。銅濃度を150g/lより上げるのは相当な高温が必要となり現実的ではない。
塩素濃度は1~100ppm、特に10~50ppmが好ましい。塩素濃度が1ppm未満となると後述する添加剤の効果を出すことが困難となり、100ppmを超えると正常なめっきが困難となる。
上記の電解条件は、それぞれの範囲から、銅の析出、めっきのヤケ等の不具合が起きないような条件に便宜調整して行う。
本発明では、ジ又はポリハロゲン化鎖式脂肪族飽和炭化水素化合物と1又は2以上のエーテル結合を有するジ又はポリハロゲン化鎖式脂肪族飽和炭化水素化合物を組み合わせたものと2個の窒素原子を有するヘテロ環式化合物の反応生成物を用いることも出来る。さらには、上記の原料化合物にジメチルアミン、ジエタノールアミン、エチレンジアミン、等の脂肪族アミノ化合物、フェニレンジアミン等の芳香族アミノ化合物、スクシニルクロリド、グルタリルクロリド、フマリルクロリド、ジクロロキシリレン、フタロイルクロリド等の複数の反応性基を有する化合物を第三原料として加えて反応した生成物を用いることもできる。但し、エピクロロヒドリン等のエピハロヒドリンを第三反応成分に用いることは反応生成物の所期の効果が得られないという点で好ましくない。
電解めっき液に添加する上記添加剤、特に上記レベラーは銅箔中に不純物として取り込まれない特性を有している。
前記色調が80%未満であると結晶は再結晶し難い状況となり、熱処理を行った際結晶が大きくならず、また結晶方位の違う結晶がランダムに存在することとなり、その結果、結晶すべりなどが悪くなり屈曲性も悪くなる傾向を示すからである。
式1:LMP=(T+273)*(20+Logt)
ここで、20は銅の材料定数、Tは温度(℃)、tは時間(Hr)
この加熱後に、前記したX線回析にて測定した(111)面に対し(331)面の相対強度が15以上となることが好ましい。
また、上記加熱処理を行った時、引張強さ20KN/cm2以下であり、0.2%耐力は10KN/cm2以下であることが好ましい。なお、耐力は8KN/cm2以下であることが最適である。
〔Niめっき〕
NiSO4・6H2O 10~500g/l
H3BO3 1~50g/l
電流密度 1~50A/dm2
浴温 10~70℃
処理時間 1秒~2分
PH 2.0~4.0
NiSO4・6H2O 10~500g/l
Na2Mo04・2H2O 1~50g/l
クエン酸3ナトリム2水和物 30~200g/l
電流密度 1~50A/dm2
浴温 10~70℃
処理時間 1秒~2分
PH 1.0~4.0
Na2Mo04・2H2O 1~ 30g/l
CoSO4・7H2O 1~ 50g/l
クエン酸3ナトリム2水和物 30~200g/l
電流密度 1~50A/dm2
浴温 10~70℃
処理時間 1秒~2分
PH 1.0~4.0
酸化亜鉛 2~40g/dm3
水酸化ナトリウム 10~300g/dm3
温度 5~60℃
電流密度 0.1~10A/dm2
処理時間 1秒~2分
PH 1.0~4.0
CrO3 0.5~40g/l
PH 3.0以下
液温 20~70℃
処理時間 1秒~2分
電流密度 0.1~10A/dm2
PH 1.0~4.0
実施例1~5、比較例1~3
電解液組成等の製造条件を表1に示す。表1に示す組成の硫酸銅めっき液を活性炭フィルターに通して清浄処理し、同じく表1に示す添加剤を添加し所定の濃度とした後、表1に示す電流密度で回転ドラム式製箔装置により電解製箔し、厚さ18μmの未処理電解銅箔を製造した。
実施例1~5、比較例1~3の未処理電解銅箔の内部の不純物元素量をSIMS分析において深さ方向に掘って測定した。測定元素は酸素(O)、炭素(C)、塩素(Cl),窒素(N)、硫黄(S)である。SIMS分析の測定条件は
1次イオン ::Cs+(5kV,100nA)
2次イオン :銅(Cu)63Cu-・塩素(Cl)35Cl-・窒素(N)14N+63Cu-・硫黄(S)34S-・酸素(O)16O-・炭素(C)12C-
スパッタ領域 :200μm×400μm
で行った。未処理電解銅箔の表面は汚れや酸化被膜の影響があるので表面から深さ方向2μmまでスパッタ除去した後に測定を開始し、深さ4μmまで分析を行った。各測定元素の強度の平均値と銅の強度の平均値から強度比を算出した。強度比の算出結果を表2に示す。
各実施例及び各比較例の未処理電解銅箔の表面粗さRz、Raを接触式表面粗さ計を用いて測定した。表面粗さRz、RaとはJIS B 0601-1994「表面粗さの定義と表示」に規定されものでありRzは「十点平均粗さ」、Raは「算術平均粗さ」である。基準長さは0.8mmで行った。測定結果を表2に示す。
各実施例及び各比較例の未処理電解銅箔を前記式1のLMP値が9000以上となる、320℃、1時間、窒素雰囲気中で加熱処理を行った。
各実施例及び各比較例の未処理電解銅箔を前記加熱条件で加熱処理した後、銅箔の断面を電子顕微鏡で撮影し、50μm×50μmの範囲内で結晶粒の最大長さが5μm以上の結晶が占める割合を測定・算出した。断面結晶粒の観察結果を表3に記載する。
前記したとおりである。EBSP分析結果を表3に記載する。
前記したとおりである。X線回析による相対強度の算出結果を表3に記載する。
各実施例及び各比較例の未処理電解銅箔を前記加熱条件で加熱処理した後、長さ6インチ×幅0.5インチの試験片に裁断し引張試験機を用いて0.2%耐力、及びヤング率を測定した。なお、引張速度は50mm/minとした。引張試験結果を表4に記載する。
0.2%耐力とは、歪と応力の関係曲線において、歪が0%の点において曲線に接線を引き、その接線と平行に歪が0.2%の点に直線を引いたその直線と曲線が交った点の応力を断面積で割ったものである。引張試験結果を表4に記載する。
各実施例及び各比較例の未処理電解銅箔と厚さ25μmのポリイミドフィルムを330℃、20分間の加熱条件でプレス圧着してポリイミドフィルム貼付電解銅箔を作成した。得られたポリイミドフィルム貼付電解銅箔を回路パターンにエッチングし、通電部を残して回路形成面に厚さ25μmのポリイミドカバーフィルムを300℃、20分間の加熱条件でプレス圧着してMIT屈曲試験サンプルを得た。得られたサンプルについて下記の条件にて回路が破断するまで屈曲試験を行った。
屈曲性の評価は、最低屈曲回数を示した比較例1の銅箔に屈曲回数を1としたときの倍数にて相対評価とした。屈曲試験結果を表4に記載する。
屈曲半径R :0.8mm
屈曲角度 :±135°
屈曲速度 :175回/分
荷重 :500g
本実施例では、不純物の分布割合、結晶粒径、同一結晶方位系などの因果関係において多少屈曲特性の状態等は変わってはいるが、比較例の銅箔と比較すると明らかに屈曲特性が向上していることがわかる。
特に、耐力と屈曲性との間には相関関係が明らかにあり、不純物または結晶粒径の大きさが耐力を下げる原因となっていることが推定できる。
また、本発明は該電解銅箔を用いた柔軟性・屈曲性を有するCCLに対応することができる。
特に、電解銅箔においては、該電解銅箔とポリイミドフィルムとを貼り付ける際にかかる熱履歴において、機械的特性、柔軟性が改良され、電気機器の小型化に対し対応できるCCL用の電解銅箔を、圧延銅箔に比べて安価に提供することができる。
Claims (8)
- 電解銅箔に式1に示すLMP(Larson-Miller parameter)値が9000以上となる加熱処理を施した後の結晶構造がEBSP(Electron Backscatter Diffraction Pattern)の分析で面に対する赤系・青系のいずれかの色調が80%以上を占める電解銅箔。
式1:LMP=(T+273)*(20+Logt)
ここで、20は銅の材料定数、Tは温度(℃)、tは時間(Hr) - 前記加熱処理を施した電解銅箔の、X線回析における(111)面に対し(331)面の相対強度が15以上であることを特徴とする請求項1に記載の電解銅箔。
- 前記加熱処理を施した後の結晶構造が、結晶粒径5μm以上の結晶粒が70%以上で、X線回析において(111)面に対し(331)面の相対強度が15以上である請求項1に記載の電解銅箔。
- 前記加熱処理を施した前記電解銅箔が、引張強さ20KN/cm2以下であり、0.2%耐力が10KN/cm2以下である請求項1~3のいずれかに記載の電解銅箔。
- 前記電解銅箔の断面に含まれる不純物は、銅箔断面の深さ方向のSIMS(Secondary Ion Mass Spectrometry)分析における銅(Cu)との強度比で少なくとも塩素(Cl)は0.5%未満、窒素(N)は0.005%未満、硫黄(S)は0.005%未満であることを特徴とする請求項1~4のいずれかに記載の電解銅箔。
- 前記電解銅箔の少なくとも片方の表面粗さが、Rz=1.5μm以下である請求項1~5のいずれかに記載の電解銅箔。
- 前記電解銅箔の少なくとも片方の面に密着性・耐熱性・耐薬品性・防錆を目的とした表面処理層が設けられている請求項1~6のいずれかに記載の電解銅箔。
- 請求項1~7のいずれかに記載の前記電解銅箔を絶縁基板に積層したことを特徴とする銅張積層板。
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JPS527819A (en) * | 1975-07-10 | 1977-01-21 | Furukawa Electric Co Ltd:The | Process for smooth electrodeposition of copper |
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WO2004059040A1 (ja) * | 2002-12-25 | 2004-07-15 | Nikko Materials Co., Ltd. | 特定骨格を有する四級アミン化合物重合体及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 |
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TWI394659B (zh) * | 2005-07-27 | 2013-05-01 | Nippon Steel Chemical Co | 高屈曲性可撓性覆銅積層板之製造方法 |
JP4781930B2 (ja) | 2005-07-27 | 2011-09-28 | 新日鐵化学株式会社 | 高屈曲性フレキシブル銅張積層板の製造方法 |
JP4224086B2 (ja) * | 2006-07-06 | 2009-02-12 | 三井金属鉱業株式会社 | 耐折性に優れた配線基板および半導体装置 |
JP5351012B2 (ja) * | 2007-04-20 | 2013-11-27 | Jx日鉱日石金属株式会社 | リチウム二次電池用電解銅箔及び該銅箔の製造方法 |
JP2010018885A (ja) * | 2008-06-12 | 2010-01-28 | Furukawa Electric Co Ltd:The | 電解銅皮膜、その製造方法及び銅電解皮膜製造用の銅電解液 |
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2009
- 2009-07-07 JP JP2009160836A patent/JP4827952B2/ja active Active
- 2009-07-07 WO PCT/JP2009/062362 patent/WO2010004988A1/ja active Application Filing
- 2009-07-07 KR KR1020117002900A patent/KR101295138B1/ko active IP Right Grant
- 2009-07-07 US US13/003,159 patent/US20110171491A1/en not_active Abandoned
- 2009-07-07 EP EP09794432.6A patent/EP2312020A4/en not_active Withdrawn
- 2009-07-07 CN CN2009801325671A patent/CN102124148B/zh active Active
- 2009-07-07 TW TW098122901A patent/TWI463038B/zh active
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JPS527819A (en) * | 1975-07-10 | 1977-01-21 | Furukawa Electric Co Ltd:The | Process for smooth electrodeposition of copper |
JP2004250777A (ja) * | 2002-06-03 | 2004-09-09 | Shipley Co Llc | レベラー化合物 |
JP2004035918A (ja) * | 2002-07-01 | 2004-02-05 | Nippon Denkai Kk | 電解銅箔の製造方法 |
WO2004059040A1 (ja) * | 2002-12-25 | 2004-07-15 | Nikko Materials Co., Ltd. | 特定骨格を有する四級アミン化合物重合体及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 |
JP2006057177A (ja) * | 2004-07-23 | 2006-03-02 | C Uyemura & Co Ltd | 電気銅めっき浴及び電気銅めっき方法 |
JP2007146289A (ja) * | 2005-10-31 | 2007-06-14 | Mitsui Mining & Smelting Co Ltd | 電解銅箔の製造方法、該製造方法で得られる電解銅箔、該電解銅箔を用いて得られる表面処理銅箔及び該電解銅箔又は該表面処理銅箔を用いて得られる銅張積層板 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2654111A1 (en) * | 2010-12-27 | 2013-10-23 | Furukawa Electric Co., Ltd. | Lithium-ion secondary battery, electrode for secondary battery, and electrolytic copper foil for secondary battery electrode |
EP2654111A4 (en) * | 2010-12-27 | 2014-08-13 | Furukawa Electric Co Ltd | LITHIUM ION SECONDARY BATTERY, ELECTRODE FOR SECONDARY BATTERY, AND ELECTROLYTIC COPPER SHEET FOR SECONDARY BATTERY ELECTRODE |
US9603245B2 (en) | 2010-12-27 | 2017-03-21 | Furukawa Electric Co., Ltd. | Lithium-ion secondary battery, electrode for the secondary battery, and electrolytic copper foil for electrode for the secondary battery |
JP2013211492A (ja) * | 2012-03-30 | 2013-10-10 | Jx Nippon Mining & Metals Corp | 圧延銅箔、銅張積層板、フレキシブルプリント配線板及び電子機器 |
TWI633196B (zh) * | 2013-04-18 | 2018-08-21 | Jx金屬股份有限公司 | 附有銅鍍層的壓延銅箔 |
Also Published As
Publication number | Publication date |
---|---|
JP4827952B2 (ja) | 2011-11-30 |
JP2010037654A (ja) | 2010-02-18 |
KR101295138B1 (ko) | 2013-08-09 |
TW201018749A (en) | 2010-05-16 |
TWI463038B (zh) | 2014-12-01 |
US20110171491A1 (en) | 2011-07-14 |
EP2312020A4 (en) | 2014-05-28 |
KR20110042072A (ko) | 2011-04-22 |
CN102124148B (zh) | 2013-11-06 |
EP2312020A1 (en) | 2011-04-20 |
CN102124148A (zh) | 2011-07-13 |
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